Production of vinylidene fluoride



Aprill 1966 M. MIVILLE ETAL 3,246,041

PRODUCTION OF VINYLIDENE FLUORIDE Filed March 30, 1965 2 Sheets-Sheet 1 9O A0 seconds 5 8O 38 seconds 66 seconds 7O 4 l7sec0nds 1 6O u. o ll) 5 f3 2 O 50 k- 2 9 u) 5 Z 40 O Q Zseconds 30 INVENTORS. /o CHLORINE MAURICE E. MIVILLE J S J. EARLEY AGENT April 12, 1966 M. MlVlLLE ETAL PRODUCTION OF VINYLIDENE FLUORIDE 2 Sheets-Sheet 2 Filed March 30, 1965 w THOUT CHLORINE I WITH 2.5 CHLORINE O O O 5 4 3 MO TS E 293M528 Q0 TEMPERATURE (C) INVENTORS. MAURICE E. MIVILLE JAMES J. EARLEY AGENT United States Patent 3,246,041 PRUDUCTIGN @F VINYHDENE FLUORHDE Maurice Miville, Flourtovvmand James J. Earley, Springfield, Pa., assignors to Pcnnsalt Chemicals Corporation, Philadelphia, PIL, a corporation of Pennsylvania Filed vMar. 30, 1965, Ser. No. 443,959 6 Claims. (Cl. 260-6535) This is a continuation-in-part of application S.N. 143,- 826, filed October 9, 1961, now abandoned.

This invention relates to the dehydrochlorination of 1,1 fiuorochloroethane to produce vinylidene fluoride in high yields and conversions at relatively low temperatures.

The pyrolytic dehydrochlorination of 1,1-difluorochlomethane to produce vinylidene. fluoride is. well known. Under purely thermal conditions (ie in the absence of catalyst) relatively high temperatures of. the order. of 650 C. and higher are required for good reaction rates giving high conversions per pass through the reactor. At temperature below about 600 C., the reaction rate drops off sharply. Attempts to increase the reaction rate at lower temperatures such as by the use of catalysts, have met with only partial success. Thus, while catalytic materials such as activated carbon or iron, have been found to increase the reaction rate at e.g. temperatures of 500 to 600 C., they generally also promote undesired side reactions particularly the dehydrofluorination of the start ing material to give substantial quantities of the by-product CH =CFCL The proportion of these by-products increases rapidly when attempts are made to obtain relatively high conversions per pass (e.g. by increasing contact time), making it impossible to obtain the desired combination of high yields and relatively high conversions. For such reasons, despite the many advantages of operating at lower temperatures such as lower heat consumption, less costly materials of construction, fewer corrosion difiiculties and the like, there has been as far as we are aware, no commercial production of vinylidene fluoride under such conditions.

In accordance with the present invention, it has now been found that excellent yields and high conversions of vinylidene fluoride may be obtained by the dehydrochlorination of l,l-difluorochloroethane at relatively low temperatures of from 450 to 625 C. and preferably from 500 to 575 C. when the dehydrochlorination is carried out inthe presence of small, controlled amounts of free chlorine (C1 This invention also enables the dehydrochlorination of 1,l,l-difluorochloroethane to be carried out at temperatures up to about 800 C. without significant dehydrofiuorination and attendant carbonization which usually occurs at such temperatures. As will be illustrated by the examples which follow, the presence of small amounts of free chlorine causes a dramatic increase in the reaction rate resulting in a several fold increase in the conversion per pass without appreciable yield losses through the formation of by-products.

The amount of free chlorine to be employed is quite critical. The weight percent of chlorine, based on the weight of the starting material, 1,1;Pdifluoroch1oroethane, should range from not less than about 0.5% to not more than about 4%, and should preferably be in the range of from 1% to 3% by weight. As illustrated by the examples which follow, it has been found that when the chlorine concentration is below about /2% by weight, the increase in conversion obtained is not substantial. Chlorine concentrations above about 4% on the other hand do not'furt-her substantially increase the conversion, and have the disadvantage of increasing the formation of undesired chlorine containing by-products. Such by-products may be formed by the chlorination in situ of the starting material followed by the dehydrochlorination of 3,246,041 Patented. Apr. 12, 1 966 the chlorinated product as shown in the following equations:

Equation A Provided the chlorine concentration is held withinthe specified limits, the yield'losses due to the above reactions are not significant, usually less than about 2%. In the preferred range of chlorine concentration, viz. from about 1 to 3%, there is obtained the optimum combination of high conversions to CH =CF and the minimum amounts of chlorination by-products.

As stated previously, the invention is carried out with advantage at temperatures of 450 to 800 C. At temperatures of about 450 C. conversions to vinylidene fluoride are'on the order of about 20% and for this reason; somewhat higher temperatures will usually be employed; The optimum combination of relatively low temperature operation coupled with high conversions and excellent yields of vinylidene fluoride at practicable contact times is generally obtained in the preferred range of from525 volume of gas per second (calculated at STP)v fed to the heated zone On the above basis, contact times useful in the process of the invention will generally lie in therange of from about one second to one hundred seconds and preferably in the range of from five'to fifty'seconds. Choice of optimum contact time will of'course involve an economic balance between the higher conversions obtained at longer contacttime and thesmaller reactor volume required at lower contact time.

It is preferred to carry out the pyrolysis reaction by continuously passing the starting material pre-mixed'jwitli a-small amount of chlorine through a heated zone. Conveniently, the heated zone may be in the form of a hot tube heated to the desired temperature by electrical or other suitable heating means. The tube should be constructed of materials resistant. to attack by the reactants or reaction products at the operating temperature, and which do not catalyze the dehydrofluorination of 1,1-difluorochloroethane. Suitable materials inthese respects include, for example, platinum, platinum and rhodium alloys, nickel, inconel, and monel. Nickel or nickel lined tubes and inconel tubes are particularly preferred for their relatively low cost and satisfactoryperformance.

The preferred starting material is 1,1,1-difluorochloroethane, CH CP Cl, although if'desired, the isomeric form 1,1-difluoro-2-chloroethane, CH ClCF H may also be used. 1,1,1,-difluorochloroethane is readily prepared by the fluorination of methyl chloroform or by the addition ofhydrogen fluoride to acetylene-followed by chlorination and is preferred for its availability and relatively. low cost.

EXAMPLES 1 TO- 15 The following examples illustrate the effect of chlorine concentration at a constant temperature of 550 C. and

3 4 at varying contact time. In these runs, the pyrolysis is EXAMPLES 16 T 21 carried out in nickel tubes having an inside diameter and heated length as shown in Table I. The tubes in each hl f 2 d case are heated electrically and the reaction temperature is onne concentratlog O 0 an a f j i recorded by thermocouples attached to the outside tube tune of f dat Varymgftempergtureis. 111 6 wall. The starting material CH CF Cl is fed to the heated tube havmg an mslde lanieter o 1 me an 6 tube at a rate corresponding to the Contact time Shown cally heated length of 36 111631165 was used 1n each case. in Table I, while chlorine is metered into the CH CF CI In Examples 16 to chlonne was added Whlk? stream and pre-mixed therewith upstream from the reac- Examples 19 to 21 at slmflar temperature 25% by Welght tor tube at a rate adjusted to give the weight percent 10 C12 based on the sfamng 'f CH3CF2p1waS chlorine as Shown in Table L The product Stream is mixed with the startmg material before passing through The following examples are carried out at a constant scrubbed in Water and caustic to remove HCL HF, and the pyrolysis tube. Product compositions were deterany residual chlorine, dried and collected. The product filmed as In the PYeVlOus P compositions are determined by feeding samples of the The data from these runs 18 Shown 111 Table and 15 product stream to a gas-liquid partition chromatograph 15 plotted graphlcally 1n FIGURE 2 of the drawmgs to and are shown in Table I. which reference is now made. In FIGURE 2, curve 6 T able I Reactor Product composition, mole percent Mole percent Example Temp- Percent C12 Contact, conversion perature, I.D., Heated by wt. based time, seconds to 0. inches length, on ST]? OH CFz CHBOF GI CH =CFCl CF= OHCl Other CH2=OF2 inches CH CF Ol l OHaOF impurity in CHSOFZCI starting material. 2 CF2=CCI2.

The critical effect of chlorine concentration within the shows the results obtained where no chlorine is added to limits of from about /2 to 4% C1 on the conversion of the starting material, while curve 7 shows the dramatically starting material to vinylidene fluoride is clearly shown 40 increased conversions that are obtained at similar temby the data of Table I. For a better understanding of this perature's with the addition of 2.5% by weight of chlorine.

Table II Reactor Product composition, mole percent Mole percent Example Temp- Percent Oi; Contact, conversion perature, I.D., Heated by wt. based time, seconds to 0. inches length, on STP CH =CF2 CHaCFzCl CH =CFC1 CFz=CHCl Other CHFOFZ inches CHzCFgCl 500 1.0 36 0.0 36 7.3 92.2 0.2 0.3 7.3 525 1.0 36 0.0 36 16.2 33.3 0.2 0.3 16.2 550 1.0 36 0.0 36 21.4 76.2 0.3 2.1 21.4 500 1. 0 36 2. 5 36 59. s 37. 6 0. 2 H 0. 3 59.8 525 1.0 36 2 5 36 66.6 31.2 0.2 B 0.2 66.6 550 1.0 36 2.5 36 78.1 20.1 0.1 0.5 73.1

1 CHSCHFQ impurity in CHaOFzCl starting material. 2 011 01 impurity in GHaCFgO]. starting material. 8 CF =CCl relationship, reference is now made to FIGURE 1 of As shown by the foregoing examples, excellent yields the drawings which shows the percent conversion of of vinylidene fluoride are obtained, the yield losses due CH CF Cl to vinylidene fluoride as a function of chlorine to the production of chlorinated lay-products being genconcentration based on the data shown in Examples 1 to erally less' than about 2%. It may be noted also that 15. Curves 1, 2, 3, 4 and 5 represent respectively the the production of vinylidene fluorochloride, CH CFCI conversions obtained at contact times of 2 seconds, 17 (produced by dehydrofluorination of the starting maseconds, 38 seconds, 66 seconds and 130 seconds at STP. terial), is negligible. Indeed, the presence of the free As is apparent from these curves, as the chlorine concenchlorine appears to have a suppressing effect upon the tration increases from 0 to about 4%, the percent conproduction of this by-product. For instance, compare version increases dramatically, the most rapid increase Examples 18 and 21 run under identical conditions exoccurring between about 0 and 2%. After the chlorine cept for the presence of 2.5% chlorine in Example 21.

concentration has reached about 4%, the rate of increase In Example 18, without chlorine, 0.3% CHCFC1 was in conversion has leveled off and no significant further in- 7 0 obtained at a 21.4% conversion, representing a 1.4%

crease in conversion is obtained by the use of higher chloyield loss. In Example 21 on the other hand, with 2.5% rine concentrations. Thus, additional chlorine results chlorine, only 0.1% CHFCFCI was obtained at a cononly in yield losses due to undesired chlorination side reversion of 78.1%, representing only a 0.1% yield loss. actions without corresponding benefit from increased In view of the suppression of dehydrofluorination of conversion. the starting material by the presence of chlorine, the

process may be operated at higher temperatures without the adverse effects normally obtained. When dehydrofluorination of the 1,1,1-difiuorochloroethane occurs it need not stop with the formation of CHFCFCI, but further dehydrofluorination can occur to form the unstable acetylenic compound which decomposes to carbon and HCl. This carbonization is quite undesirable because it may plug the reactor tubes and aflect operability of the process. However, by use of chlorine in accord with this invention, temperatures up to about 800 C. in conjunction with low contact time may be used Without significant dehydrofluorination and carbonization occurring. Operation of the process at the higher temperatures and low contact time (i.e. higher thruput) is desirable because it permits a very eflicient process to be achieved.

The following example illustrates the favorable operation of the process at the higher temperature.

EXAMPLE 22 Using a reactor having an inside diameter of 2.0 inches heated for a length of 8'2", a mixture of 1,1,1-difluorochloroethane and 1.8% chlorine was fed in at 140 lbs./ hr. and was pyrolyzed at 649 C. at a contact time (STP) of 1.4 seconds. The percent conversion of vinylidene fluoride was 48.1%.

When operated without chlorine being present under the above conditions the conversion to vinylidene fluoride is on the order of about 10%.

EXAMPLE 23 Using a 12" length of 4;" nickel pipe having an inside diameter of 0.68 cm. as a reactor (tube volume 11.3 cc.) 1,1,l-difluorochloroethane was fed in at a rate of 300 g./hr. and at 800 C. for a contact time of 0.15 sec. whereby 25.7 mole percent of vinylidene fluoride was formed.

When the reaction was repeated using 1.5% chlorine admixed with the 1,1,l-difluorochloroethane, the product was obtained at 54 .3% conversion.

We claim:

1. A method for producing vinylidene fluoride by the dehydrochlorination of 1,1,1-difluorochloroethane which comprises the step of passing a stream of said fluorochloroethane containing from about 0.5% to 4% by weight of free chlorine through a zone heated to a temperature of from 450 to 800 C.

2. A method in accordance with claim 1 in which said stream contains from 1 to 3% by weight free chlorine.

3. A method in accordance with claim 1 in which said zone is heated to a temperature of from 525 to 575 C.

4. A method for producing vinylidene fluoride by the dehydrochlorination of 1,1,1-difiuorochloroethane which comprises the step of passing a stream of said fluorochl-oroethane containing from about 1 to 3% by weight of free chlorine through a Zone heated to a temperature of from 525 C. to 575 C.

5. A method for producing vinylidene fluoride by the dehydrochlorination of 1,1,l-difluor-ochloroethane which comprises the step of passing a stream of said fluorochloroethane containing from about 0.5 to 4% by weight of free chlorine through a tube heated to a temperature of from 450 C. to 800 C. at a contact time of from about 5 to seconds.

6. A method for producing vinylidene fluoride by the dehydrochlorination of 1,1,1-difluorochloroethane which comprises the step of passing a stream of said fluorochloroethane containing from about 1 to 3% by weight of free chlorine through a tube heated to a temperature of from 525 to 575 C. at a contact time of from about 5 to 50 seconds.

References Cited by the Examiner UNITED STATES PATENTS 2,378,859 6/1945 Mugdan et al. 260-656 2,566,807 9/1951 Padbury et a1. 260-6535 2,627,529 2/ 1953 Feasley et al. 260653.5

DANIEL D. HORWITZ, Examiner.

LEON ZITVER, Primary Examiner. 

1. A METHOD FOR PRODUCING VINYLIDENE FLUORIDE BY THE DEHYDROCHLORINATION OF 1,1,1-DIFLUOROCHLOROETHANE WHICH COMPRISES THE STEP OF PASSING A STREAM OF SAID FLUOROCHLOROETHANE CONTAINING FROM ABOUT 0.5% TO 4% BY WEIGHT OF FREE CHLORINE THROUGH A ZONE HEATED TO A TEMPERATURE OF FROM 450* TO 800*C. 